Monoazo pigments containing a benztriazole radical



United States Patent 3,498,966 MONOAZO PIGMENTS CONTAINING ABENZTRIAZOLE RADICAL Willy Mueller, Riehen, Switzerland, assignor toClba Limited, Basel, Switzerland, a company of Switzerland No Drawing.Filed Mar. 14, 1967, Ser. No. 624,972 Claims priority, applicationSwitzerland, May 11, 1966, 6,881/ 66 Int. Cl. C09b 29/22; C08g 51/66;C09d 7/12 US. Cl. 260-157 9 Claims ABSTRACT OF THE DISCLOSURE Monoazopigments which are obtained by coupling the diazo compound of anaromatic amine, especially an amino-benzene, with a 2,3-hydroxynaphthoic acid arylide, the arylide radical of which contains abenztriazole radical. The azo pigments are useful for dyeing for exampleplastics, lacquers and spinning solutions in orange to red tints whichare fast to light and migration.

The present invention is based on the observation that new and valuablemonoazo pigments of the formula CONHRs in which R represents the residueof a diazo component free from groups imparting solubility in water, Rrepre sents a naphthalene residue in which the azo, hydroxyl andcarboxylic acid amide groups are in 1,2,3-position and R represents aresidue of the formula in which R represents a benzene or a naphthaleneresidue which is fused to the triazole residue through two adjacentcarbon atoms and R represents an aryl residue, may be obtained when (a)a carboxylic acid halide of the formula COHal is condensed with an amineof the formula or (b) a diazo compound of an aromatic amine is coupledwith a naphthol of the formula Since the products of the invention arepigments, they must not contain groups imparting solubility in water,particularly acidic groups imparting solubility in water, for example,sulphonic acid or carboxylic acid groups.

3,498,966 Patented Mar. 3, 1970 Specially valuable products may beobtained when carboxylic acid chlorides of the formula are used asstarting materials.

The carboxylic acids from which the halides are derived may be obtainedby coupling a diazo compound of an aromatic amine, preferably anaminobenzene, especially one of the formula X COOH in which X representsa hydrogen or a halogen atom or an alkoxy group.

The following may be mentioned as examples of aminobenzenes of theFormula 5: aniline, and especially halogenated anilines, for example,2-, 3- or 4-chloroaniline, 3,4 dichloroaniline, 2,3 dichloroaniline,2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline,2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-, 3- or4-bromoaniline, 2,4-dibromoaniline, 2,5-dibromoaniline, Z-methyl- 5chloroaniline, 2 methyl-4-chloroaniline, 2-methyl-3- chloroaniline,2-chloro-S-trifiuoromethylaniline, furthermore, nitroanilines, forexample, 2-, 3- and 4-nitroaniline, 4-chloro-2-nitroaniline,2-chloro-4-nitroaniline, 4-methyl- 3 nitroaniline, 2,4dimethyl-3-nitroaniline, 2-methyl-5- nitroaniline,2-methyl-4-nitroaniline, furthermore, alkoxyanilines andphenoxyanilines, for example, 2- and 4-mothoxyaniline, 2- and4-ethoxyaniline, 3-chloro-4-methoxyaniline, 2 methoxy S-nitroaniline,Z-methoxy-S-chloroaniline, 2 methoxy S-trifluoromethylaniline,2-amino-4- trifiuoromethyl-4'-chlorodiphenylether, 2nitro-4-ethoxyaniline, 2-methoXy-4-chloro-S-methylaniline, 2-amino-4-chlorodiphenylether, 2 amino-2,4-dichlorodiphenylether,

, Z-amino-4,4-dichlorodiphenylether, and also 1-amino-2- in which Vrepresents a halogen atom or an alkyl, alkoxy or carbalkoxy group, W andZ each represents a hydrogen or halogen atom and Z and 2,; eachrepresents a hydrogen or halogen atom or an alkyl, alkoxy, nitro, cyano,carbalkoxy or trifluoromethyl group.

The following may be mentioned as examples:

4-methyl-3 -aminobenzoic acid-2-chloro-5 '-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2',5'-dichloroanilide,

4-chloro-3-aminobenzoic acid-2'-chloro-5-carbomethoXyanilide,

4-chloro-3-aminobenzoic acid-3-chloroanilide,

4-chloro-3-aminobenzoic acid-2'-chl0r0-5'-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-3'-trifiuoromethylanilide,

4-chloro-3-aminobenzoic acid-3',5-bis-trifiuoromethylanilide,

4-chl0r0-3-aminobenzoic acid-2,4',5'-trichloroanilide,

2,4-dichloro-S-aminobenzoic acid-2',5'-dichloroani1ide,

2,4-dichloro-S-aminobenzoic acid-2',4'-dichloroanilide,

2,4-dichloro-S-aminobenzoic acid-3'-trifluoromethylanilide,

2,4-dichloro-S-aminobenzoic acid-3'-chloroanilide,

5'-amino-4-methoXy-2-chlorobenzoic acid-3'-trifluoromethylanilide,

4-methyl-3-aminobenzoic acid-2',5-dichloroanilide,

4-methyl-3-aminobenzoic acid-3'-trifluoromethylanilide,

4-methoXy-3-aminobenzoic acid-3-chloroanilide,

4-methoXy-3-aminobenzoic acid-2',5'-dichloroanilide,

4-methoxy-3-aminobenzoic acid-2',4',5'-trichloroanilide,

4-carbomethoXy-3-aminobenzoic acid anilidc,

4-methoxy-3-aminobenzoic acid-3'-trifiuorornethylanilide,

4-carbethoXy-3-aminobenzoic acid-2,S'-dichloroanilide,

4-methoxy-3-aminobenzoic acid-3',5-bis-trifluoromethylanilide,

4-methoxy-3-arninobenzoic acid-2-chloro-5-trifluoromethylanilide,

4-methoXy-3-arninobenzoic acid-2,5-dimeth0xy4'-chl0- roanilide,

4-methoxy-3-aminobenzoic acid-2',5-dimethyl-4'-chloroanilide and4-methoXy-3-aminobenzoic acid-3-trifluoromethylanilide.

The azo dyestulf carboxylic acids obtained are treated with agents whichare capable of converting carboxylic acids into their acid halides, forexample, their acid chlorides or bromides, such agents being, inparticular, phosphorus halides, for example, phosphorus pentabromide orphosphorus trichloride or phosphorus pentachloride, phosphorusoxyhalides and preferably thionyl chloride.

The treatment with the said acid halogenating agents is advantageouslycarried out in an inert organic solvent, for example, indimethylforrnamide, a chlorobenzene, for example, monochlorobenzene ordichlorobenzene, toluene, Xylene or nitrobenzene, if necessary,dimethylformamide may be used in conjunction with the last five solventsspecified.

When preparing the 'carboxylic acid halides, it is generallyadvantageous first to dry the azo compounds, which are prepared in anaqueous medium, or to free them from water by azeotropic distillation inan organic solvent. If desired, the azeotropic drying may be carried outimmediately before the treatment with the acid halogenating agents.

The azo dyestuff carboxylic acid chlorides so obtained are preferablycondensed with monoamines of the formula or with monoamines of theformula The following may be mentioned as examples:

5-amino-4'-methoxy-2-phenylbenztriazole,5-amino-4-eth0Xy-2-phenylbenztriazole,5-amino-4'-carbethoxy-2-phenylbenztriazole,5-amino-4'-a-cetylamino-2-phenylbenztriazole,S-amino-6-chloro-4'-methyl-2-phenylbenztriazole,5-amino-6,2,4,5-tetrachloro-2-pheny1benztriazole,S-amino-6-methyl-2-phenylbenztriazole,5-amino-6-methyl-4'-ethoXy-2-phenylbenztriazole,S-amino-6-methyl-4'-carbethoxy-2-phenylbenztriazole,5-amino-6-methyl-2',5-dirnethoxy-4'-chloro-2-phenylbenztriazole,5-amino-6-methyl-2,5 -dim ethoxy-4'-benzoylamino-2- phenylbenztriazole,S-amind6-methyl-4'-benzoylamino-2phenylbenztriazole,5-amino-6,2'-dimethyl-4'-nitro-2-phenylbenztriazole,S-amino-6-methyl-2-methoxy-4'-nitro-2-phenylbenztriazole, l5-amino-6,2-dimethyl-4'-nitro-2-phenylbenztriazo1e,S-amino-6-methyl-2-nitro-4'-n1ethoXy-2-phenylbenztriazole,5-amino-6-methyl-3',5'-di(trifiuoromethyl)-2-phenylbenztriazole,5-amino-6-rnethyl-2'-chloro-5'-trifiu0romethyl-Z-phenylbenztriazole,S-amino-6-methoxy-4-acetylamino-Z-phenylbenztriazole,S-amino-6-methoxy-4'-benzoylamino-2-phenylbenztriazole,5-amino-6-methoxy-4'-carbomethoxy-Z-phenylbenztriazole,5-amino-6-methoxy-4'-carhethoXy-2-phenylbenztriazole, 5 -amino-6-methoxy-S '-aminosulphonyl-2-phenylb enztriazole,S-amino-6-methoxy-2'-chloro-5-trifiu0rom ethyl-2-phenylhenztriazole,S-amino-6methoxy-2'-trifluoromethyl-4'-chloro-Z-phenylbenztriazole,4-amino-5'-methyl-2-pheny1benztriazole, 4'-amino-5'-methyl-S-chloro-2-phenylbenztriazole,4'-amin0-5,5'-dimethyl-Z-phenylbenztriazole, 4-am ino-S'-methyl-5-methoXy-2-phenylbenztri azole,4-amino-2,5-dimethyl-2-phenylbenztriaz0le, 4'-amino-2',5'-dimethyl-5-chloro-2-phenylbenztriazole,

'-amino-2',5 ,5 -trimethyl-Z-phenylbenztriazole,4'-amino-2',5'-dimethyl-5-methoxy-2-phenylbenztriazole,4'-amino-2'-methyl-5 -methoxy2-phenylbenzatriazole,4'-amino-2-methyl-5'-methoXy-5-chloro-Z-phenylbenztriazole,4'-amino-2,5-dirnethyl-5'-meth0Xy-2-phenylbenztriaz0le,4'amino-2'-methyl-5,5'-dimethoxy-Z-phenylbenztriazole,4'-amin0-2,5'-dimethoxy-Z-phenylbentriazole,4'-amino-2',5-dirnethoXy-S-chloro-2-phenylbenztriazole,4'-amino-2',5'-dimethoXy-5-methyl-2-phenylbenztriazole, 4- amino-2,5 ,5'-trimethoxy-2-phenylbenztriazole,4'-amino-5-chloro-Z-phenylbenztriazole,4--amino-S-trifiuoromethyl-Z-phenylbenztriazole, 4'-amino-5 -1nethy1-5-trifluoromethyl-Z-phenylbenztriazole,4'amino-2'-chloro-S-methyl-S-trifluoromethyl-Z-phenylbenztriazole,4'-amino-2', -dimethylS-trifiuoromethyl-Z-phenylbenztriazole,4'-amino-2'-methyl-5'-methoxy-S-trifluoromethyl-Z-phenylbenztriazole,4'-amino-2,5-dimethoxy-S-trifluoromethyl-Z-phenylbenztriazole,

4-amino-2',5-diethoxy-5-trifluorornethyl-Z-phenylbenztriazole,4'-amino-2-phenylnaphthotriazole,4-amino-2'-methyl-2-phenylnaphthotriazole,4-amino-2-chloro'2-phenylnaphthotriazole,4-amino-2'-methoxy-2-phenylnaphthotriazole and4'-amino-2,5-dimethyl-Z-phenylnaphthotriazole.

Condensation between the carboxylic acid halides and the amines definedabove is advantageously carried out in an anhydrous medium. Under theseconditions it generally proceeds surprisingly easily, even attemperatures within the boiling range of the common organic solvents,for example, toluene, monochlorobenzene, dichlorobenzene,trichlorobenzene, nitrobenzene and the like. To accelerate the reaction,it is generally advantageous to use an agent capable of binding acid,for example, anhydrous sodium acetate or pyridine.

Some of the products obtained are crystalline and some are amorphous.They are generally obtained in a very good yield and in a pure state. Itis expedient first to isolate the acid chlorides obtained from thecarboxylic acids. In some cases, however, isolation of the acidchlorides may be omitted without harm and condensation may be carriedout immediately after the preparation of the carboxylic acid chlorides.

In method (b) of the process of the invention, the new pigments may beobtained by coupling a diazotized aromatic amine, preferably anaminobenzene, especially one of the Formula 5 or 10, with a naphthol ofthe Formula 6, especially one of the formula N Y x -o ONH I Y U Y1 I orof the formula to neutralize the mineral acid liberated from thediazonium salt during coupling. Coupling is advantageously carried outat a pH value of 4 to 6. The pH value is advantageously adjusted by theaddition of a buffer. Suitable buffers are, for example, the salts,especially the alkali metal salts, of formic acid, phosphoric acid orespecially acetic acid. The alkaline solution of the coupling componentadvantageously contains a wetting, dispersing or emulsifying agent, forexample, an aralkylsulphonate, for example, dodecylbenzenesulphonate orthe sodium salt of 1,1-naphthylmethanesulphonic acid, polycondensationproducts of alkylene oxides, for example, the product obtained byreacting ethylene oxide with para-tert.octylphenol, and also thealkylesters of sulphoricinoleates, for example,n-butylsulphoricinoleate. The dispersion of the coupling component mayalso advantageously contain protective colloids, for example,methylcellulose or small amounts of inert organic solvents which aresparingly soluble or insoluble in water, for example, aromatichydrocarbons which may be halogenated or nitrated, for example, benzene,toluene, xylene, chlorobenzene, dichlorobenzenes or nitrobenzenes, aswell as aliphatic halogenated hydrocarbons, for example, carbontetrachloride or trichloroethylene; also suitable are organic solventsmiscible with Water, for example, acetone, methylethylketone, methanol,ethanol or isopropanol.

Coupling may also be carried out advantageously by continuouslycombining an acidic solution of the diazonium salt with an alkalinesolution of the coupling com ponent in a mixing nozzle, during whichcoupling takes place instantaneously. Care must be taken to ensure thatthe diazo component and coupling component are present in the mixingnozzle in equimolecular amounts, but it may be advantageous to use asmall excess of the coupling component. The simplest way of doing thisis by control of the pH value of the liquid in the mixing nozzle. Caremust also be taken to ensure that the two solutions are in a state ofviolent turbulence in the mixing nozzle. The pigment dispersion formedis removed continuously from the mixing nozzle and the pigment isisolated by filtration.

The new products are valuable pigments which may be used for a very Widevariety of purposes. For example, they may be used in a state of finedivision for the spincolouration of filament and staple-fibre viscose,cellulose ethers, cellulose esters, polyamides, polyurethanes and polyesters, and also in the production of coloured laquers andlake-formers, solutions or products made from acetylcellulose,nitrocellulose, natural or synthetic resins, for example, polymerizationresins or condensation resins, for example aminoplasts, alkyd resins,phenoplasts, polyole fines, for example, polystyrene, polyvinylchloride, polyethylene, polypropylene, polyacrylonitrile, rubber,casein, silicones and silicone resins. They may also be usedadvantageously in the manufacture of coloured pencils, cos- 168 parts ofthe dyestufi obtained by diazotisingS-trifluoromethyl-Z-chloro-l-aminobenzene in aqueous hydrochloric acidwith sodium nitrite and coupling with 2,3- hydroxynaphthoic acid areheated for one hour at to C., while stirring, in admixture with 1,000parts of ortho-dichlorobenzene, 70 parts of thionyl chloride and 5 partsof dimethylformamide. After cooling the reaction mixture, themonocarboxylic acid chloride of the dyestuif is isolated by filtration,washed with cold benzene and dried in vacuo at 40 to 50 C.

8.3 parts of the acid chloride so obtained are heated for 12 hours at to0. in admixture with 6.2 grams of6-amino-5-methoXy-2-(4'-acetylaminophenyl)- 2,1,3-benztriazole and 400parts of ortho-dichlorobenzene. The batch is then filtered at 100-120 C.and the pigment which is isolated is Washed with ortho-dichlorobenzeneat 130 C. until the filtrate runs practically colourless. Subsequently,it is Washed with methanol until all the dichlorobenzene has beenremoved and then with hot water; it is dried in vacuo at 90 to 100 C.The product obtained corresponds to the formula HO CONE-- can be reactedin the manner described film are indicated in Column IV.

in the first and second paragraphs of the above example via theorresponding carboxylic acid chlorides With 1 mol of theaminobenztriazole components listed in Column III. The tints which thepigments produce in polyvinyl chloride Number Diazo component Couplingcomponent Aminotriazole Tint in PVC 1 2-chloro5-trifluoro-methyleniline2,3-hydroxynaphthoic acid 5-methyl-6-emino-4-carbethoxy-2- Scarlet.

phenylbenztriazole. 2 d do -methyLfi-amino-4-nitro-2 methoxy-Scarlet-red.

2-phenylbenztriazo1e. 3 do do 5-methyl-Gemino-4-Inethyl-2-nitr0-2-Scarlet.

phenylbenztriazole. 4 d0 do 6 mcthoxy-fi-amino-4-methoxy-2- Yellowishscarlet.

phenylbenztriazole. 5 2,4,5-trichlor0aniline do5-metl1oxy-fi-amindy-acetylamino- Red.

phenylbenztriazole. 6 d0 do 5-methyl-tamin r-4'-earbeth0xy-2- Brown-red.

phenylbenztriazole. 7 do do frmethyl-fS-emino-2-nitro-4'-methyl-2-Bluisli red.

phenylbenztriazole. 8 do do 5-meth0xy-6amino-4-methoxy-2- Scarlet redphenylbenztriazole. 9 2,5-dic-hl0r02miline -d0 do Orange. 10 do dofi-methoxy-fi-amin0-4-earbethoxy-2- Red.

phenylbenztriazole. 11 do do 6-emino-4-carbethoxy-Z-phenylbenz- D0.

triazole. 12 do d0 S-methyl-G-aminc-4'-carbethoxy-2- Yellowish red.

phenylbenztriazole. do l.. d0 5-chloro-6-amin0-4-carbethoxy-2- Orange.

phenylbenztriazole. 14 4-nitr0-2-trifluoro-methylaniline do5-methoxy-fi-emino-4-carbethoxy-2- Bluish red.

phenylbenztriazole. 15 Z-nitrc-4-trifluoromethylaniline d0 do Red. 16 dodo 5-111ethyl-fi-aminoy-eerbethoxyfi- Scarlet.

phenylben ztriazole. 17 do do 6-aminc-4'-carbethoxy-Z-phenylbenz-Orange.

triazole. 18 .do .110 5-chlo1'0-6-amino--l-carbethoxy-2- Yellowishorange.

phenylbenztriazole. 19 do do (Seminal- Y-carbarnido-Z-phenylbenz-Orange.

triazo e. 20 2-an1ino-4trifiuoromethyldiphenyl d05-ehloro-fi-ainino-4-acetylamino-2- Scarlet.

ether. phenylbenztriazole. 21 -do do 5-methyl-ttemino-Q-methoxy-l-Scarlet red.

phenylbenztriazole. 22 B-aminobenzoie acid methylester d05-1nethoxy-6-amin0-4-benz0ylamino Red.

Z-phenylhenztriazole. 23 do do S-Inethoxy-6-amino4-earbeth0xy-2- Do.

phenylbenztriazole. 24 5chilzoro-2aminobenzoic acid ethyl d0 doRed-brown.

es er. 25 2,5-dichl0roaniline 6-1)romo-2,3-hydroxynaphthoic acid doBlue-red 26 .do G-methcxy-Z,3-hydroxynaphthoic .do Brown.

aei 27 4-methyl-3-aminobcnzoic acid-2'- 2,3-hydroxynaphthoic acid6-amino-fiethoxy-Z-phenylbenz- Scarlet red.

chl01'0-5-trifluoro1nethylanilide. triazole. 28 do do5methyl-6-amiiio-4-acctylamino-2- Red.

plienylbenztriazole. 29 do d0 fi-methyl-fiamino-Z',5-dimeth0xy-4- Bluishred.

chloro-2phenylbenztriezole. 30 d0 .do 5-111ethyl-fi-amino-4-ethoxy2phenyl- Do.

benztiiazolc. 31 do .-do (i-amin0l-4-methoxy-2-phenylbenz- Scarlet Red.

' triazo e. 32 4-methyl-3-aminobenzoic acid-2,5- .do do Scarlet.

dichloroanilide. 33 .-do d0 5-methyl-6-amino-i-ethoxy-2-phenyl- Red.

benztriezole. 34 do do 5-methyl-6 arninc-2,5dimeth0xy-4'- Bluish red.

ehloro-2-phenylbenztriazole. 35 do do fi-stiminci--carbetmXy-Z-phenylbenZ- Brown-orange.

riazo e. 1 -do 5-ehl01'06-amino-4-carbethoxy-2- Red.

ph enylbenztriazole. 37 d0 ..d0 5-methoxy-6-an1ino-4-carbethoxy-Z- D0.

phenylbenztiiazole. 38 do .d 5-mcthyl-6-arnino-4-carbethoxy-2- Do.

phenylbenztriazole. 39 do do 5-methyl-6-amino-2-methoxy-4-nitro- Orange.

2-phenylbenztriazole. 4O do .do 5-methyl-6emino4-benzoylemino-2- Bluishred.

phenylbenztriazole. 41 do do 5methoxy-6-amino-3-aminosul- Scarlet.

phonyl-Z-phenylbenztriazole. 42 4-methyl-3-am1nobenzo1c ac1d-2,4',5- dosehloro-c-amino-fz,4,5-trichloro2- Bluish red.

triehloroanilide. phenylbenztriazole. 43 ..d0 -d05-methoxy'GeminoA'eeetylemino-Q- Red.

phenylbenztriazole. 44 do d0 dmethyl-damino-Wjdi(trifluoro- Bluish red.

methyl)-2-phenylbenztriazole. 45 "do d0 fi-Inethoxy-damino-earbethoxy-Z- Red.

phenylbenztriazole. 46 d0 d0 6amin0-4-carbethoxy-Zphenylbenz- Do.

triazole. 47 do d0 5-chloro-6-amino-4'-carhethoxy-2- Do.

phenylbenztriazole. 48; .do J10 5-metlryl-6-emino-4-carbethoxy-2- D0.

phenylbenztriazole. 49 do .130 5methyl-fi-amino-4-benzoylaminc-2- Bluishred.

plienylbenztriazole. 50 do .d0 5-rnetl1oxy-fi-amino-W-aminosul- Scarlet.

phonyl-Z-phenylhenztriazole. 51 d0 do 5m]ethyl-G-amino-2-methcxy-4-Bluisli red.

nitro-Q-phenylbenztriazole.

Number Diazo component Coupling component Aminotriazole Tint in PVC 5..4-eh1oro-3-aminobenzoic acid-3- do 5emethyl-6-amino 2,5dimethoxy4-Scarlet.

chlro-2-methylani1ide. benzoylamino-2-phenylbenztriazole. dofi-methyl-B-amino-Z,5-dimethoxy-4- Do.

ehloro-2-phenylbenztriazole. 54 .-d0 ..do-Inethyl-tiamino-4-ethoxy-2-phenyl- Do.

bonztriazole. 55 d0 do 5-111ethyl-G-aminn-4'-acetylamino-2- Orangephenylbenztrlazole. 5-ch1oro-6arnir1o-2',4,5-trichloro-2- Do.

phenylbonztriazole. 5-ruethyl-6-arnino-4-benzoylamino-2- Scarletphenylbenztriazole. 5-methyl-damlno-W-methoxy-Q- Red.

nitro-Z-phenylhenztriazole. 5-methyl-S-amino-2-nitro-4-methyl-2- Do.

phenylbenztriazole. 5-methoxy-fi-amino-4-carbethoxy-Z- Orange.

phenylbonztriozole. 5-methyl-6-amino-3'-trifluoromethyl- Scarlet.

2-phenylbenztriazole. (ramino-4-earbethoxy-2-phenylbenz- D0.

triazole. ochloro-6-amino 4'-earbethoxy-2- D0.

phenylbenztriazole. G-amino-4-carbamido-Z-phenylbenz- Red.

triazole. 5-111ethyl-tl'amin0-4'carbethoxy-2- Scarlet.

phenylbenztriazole. 2,6'-dimethoxy-4-amino-2-phenyl- Brown.

benztriazole. 67 a-methoxyii'aminobenzoic acid-3- do5-methoxy-6-amin0-4-methoxy-2- Carmine,

trifiuoromethylanilide. phenylbenztriazole. 68 do --d06-amino-4ethoxy-Z-phenylbenz- Do.

triazole. 69 do ..d0 5methyl 6-amino-4-acety1amino-2- Blue-red.

phenylbenitriazole. 70 do d0 5 methyl-6*arnino-2,5-dimethoxy-4- Do.

chloro-Z-phenylbenztriazole. 71 do -.d05-methyl-6-21mino-4-ethoxy-2-phenyl- Carmine.

benztriazole. 72 do .do G-amino-4-methoxy-2-phenylbenz- Do.

triazole. 73 -do ..do 5chloro-6-amino-4-carbethoxy-2- Blue-red.

phenylbenztriazole. 74 do -d0 5-methyl-6-an1ino-3',5-di(trifluoro- Do.

methyl)-2-phenylbenztriazole. 75 ..do "do5-methoxy-tramino-t-carbethoxy-z Carmine.

phenylbenztriazole. 76 d0 d0 5methoxy-fi-emino-4-acetylamino-2- Do.

phenylbeuztriazole. 77 do d0 5-methyl-6-amino-4-carbethoxy-2- Do.

phenylbenztriezole. 78 do d0 5-methyleamino-2-methoxy-4-nitro- Bluishred.

2phenylbenztriazole. 79 2,5-dimethoxy-t-benzoylaminoaniline .1105-methyl-damiuo-y-carbethoxy-2- Navy blue.

phenylbenztriazole. 80 2,E-diethoxy-tbenzoylaminoaniline -.do5-methoxy-6-amino-4-acetylamino-2- Blue.

phenylbenztrlazole. 81 4methyl-3-aminobenzoic acid-2,4,5- -d02-(4eminopheny1)-naphthotriazole Do.

trichloroanilide. 8.. 2-ch1oro-5-trifluoromethylaniline .-do5-benzoylamino-2-(4-aminopheny1)- Do.

benztriazole.

EXAMPLE 2 45 1y, 1t 1s washed with hot water and then dr1ed 1n vacuo 8.1parts of 2,S-dichloro-l-aminobenzene are diazotized in the usual mannerwith aqueous hydrochloric acid, ice and sodium nitrite.

Meanwhile, 24.5 parts of 5-methyl-6-(2'-hydroxy-3-naphthoylarnino)-2"-chlorobenztriazole 5" carboxylic acid methylesterare dissolved in 50 parts of ethanol, parts of sodium hydroxidesolution, 200 parts of water and 100 parts ofethyleneglycolmonomethylether. 1 part of the condensation productobtained from 8 mols of ethylene oxide and 1 mol of paratertoctylphenolis added to the solution and subsequently the naphthol is precipitatedwith 70 parts of glacial acetic acid while stirring well. Coupling iseffected by addition of the diazo compound described in the firstparagraph while keeping the pH value at 3 to 4 and the temperature at toC. The batch is stirred for about 2 hours at the same temperature tocomplete the coupling, the pigment suspension formed is rendered acid toCongo paper by the addition of hydrochloric acid and then filtered. Thefilter residue is washed with hot water until chlorine ions can nolonger be detected in the filtrate.

The moist filter cake is stirred into 250 parts of chlorobeuzene, themixture is heated in a closed vessel while stirring, and the water isdistilled in admixture wilth chlorobenzene by means of a descendingcondenser. When the internal temperature has reached 132 C., the batchis cooled to 100 C., filtered, and the filter residue is washed firstwith hot chlorobenzene until the filtrate runs practically colourlessand then with cold methyl alcohol. Finalat to C. A red pigment having avery soft grain and possessing great tinctorial strength is thusobtained in good yield. The tint it produces in plasticized polyvinylchloride displays a very good fastness to light, solvents and bleeding.

EXAMPLE 3 31.0 parts of 3-amino-4-methoxybenzoic acid 3'trifluoromethylanilide are diazotized in the usual manner at 0 to 2 C.and the solution is clarified by filtration.

Meanwhile, 45.5 parts of 5-methoxy-6-(2"-hydroxy-3-naphthoylarnino)-4-ethoxybenztriazole are dissolved cold in a mixture of150 parts of ethyleneglycolmonoethylether and parts of 30% sodiumhydroxide solution. The two solutions are conducted continuously to amixing nozzle, if necessary after dilution with water, where cou plingof the components takes place instantaneously. The pH value in themixing nozzle is kept at between 5 and 6 by regulating the flow of thesolutions. The temperature must be between 35 and 40 C. The pigmentsuspension formed is filtered and the filter residue is washed with hotwater. It is then stirred for some time with a mixture comprising 20parts of water, parts of ethyleneglycolmonoethylether and 100 parts ofortho-dichlorobenzene, at a temperature of 80 to 90 C., and the batch isthen filtered. The filter residue is washed successively withethyleneglycolmonoethylether and ethanol and then dried in vacuo at 70to 80 C. A red pigment of high tinctorial strength is obtained in a goodyield. It colours 11 polyvinyl chloride bluish red tints which are fastto migration and light.

EXAMPLE 4 A mixture is prepared from 65 parts of stabilized polyvinylchloride, 35 parts of dioctyl phthalate and 0.2 part of the pigmentobtained in the manner described in the first paragraph of Example 1.The mixture is then worked to and fro for 7 minutes at 140 C. on atwo-roller mill. A scarlet film possessing a very good fastness to lightand migration is obtained.

I claim:

1. An azo pigment of the formula in which X represents a hydrogen or abromine atom or lower alkoxy group, X represents a hydrogen, chlorine orbromine atom, X; represents a hydrogen or bromine atom or lower alkyl,lower alkoxy, phenoxy, nitro, cyano, lower carbalkoxy, carbamido, loweralkanoylamino or trifiuoromethyl group; X represents a hydrogen orbromine atom or lower alkyl, lower alkoxy, phenoxy, nitro, cyano, lowercarbalkoxy, carbamido, lower alkanoylamino or trifluoromethyl group orwherein Z; represents a hydrogen or chlorine or bromine atom and Z and Zeach represents a hydrogen or chlorine or bromine atom or a lower alkyl,lower alkoXy, nitro, cyano, lower carbalkoxy or trifluoromethyl group, Yrepresents a hydrogen or a chlorine or bromine atom or a lower alkyl orlower alkoxy group and Y Y and Y each represents a hydrogen, chlorine orbromine atom or a lower alkyl, lower alkoxy, trifluoromethyl, lowercarbalkoxy, cyano, benzoylamino or lower alkanoylarnino group.

12 2. An azo pigment of the formula X2 i ('3? N X3 OH Z2 N X ooNH N Z: r\N/ in which X represents a hydrogen, chlorine or bromine atom, X and Xeach represents a hydrogen or bromine atom or lower alkyl, lower alkoxy,phenoxy, nitro, cyano, lower carbalkoxy, carbamido, lower alkanoylaminoor trifluoromethyl group, Z and Z each represents a hydrogen, chlorineor bromine atom or a lower alkyl or lower alkoxy group and Z representsa hydrogen, chlorine or bromine atom or a lower alkyl, lower alkoxybenzoylamino or trifluoromethyl group.

3. An azo pigment of the formula I CONE- I \N/ Y4 in which V representsa chlorine or bromine atom or a lower alkyl, lower alkoxy or lowercarbalkoxy group, W and Z each represents a hydrogen or chlorine orbromine atom and Z and Z each represents a hydrogen or chlorine orbromine atom or a lower alkyl, lower alkoxy, nitro, cyano, lowercarbalkoxy or trifluoromethyl group, X represents a hydrogen or abromine atom or lower alkoxy group, Y represents a hydrogen or achlorine or bromine atom or a lower alkyl or lower alkoxy group and Y Yand Y each represents a hydrogen, chlorine or bromine atom or a loweralkyl, lower alkoxy, trifluoromethyl, lower carbalkoxy, cyano or loweralkanoylamino group.

4. The azo pigment of the formula 5. The azo pigment of the formula 6.The azo pigment as claimed in claim 3 of the formula N H0 COHN lN-O-OCzHB on, N=N NHCO 00H:

7. The azo pigment as claimed in claim 3 of the formula N HO COHN/NNHCOCH$ N 8. The azo pigment of the formula HO COHN l 31 1TI=N NQQNHCO CE 9. The azo pigment of the formula References Cited UNITEDSTATES PATENTS 3,121,073 2/1964 Hertel et a1. 260146 CHARLES B. PARKER,Primary Examiner DONALD M. 'PAPUGA, Assistant Examiner US. Cl. X.R.

Case 5919/E Patent: No. 3,498,966 Dated March 3 1970 Inventor (s WILLYMUELLER It: is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 10, lines #1 and &3, "Do" should read Red Signed and sealed this3rd day of August 1971 (SEAL) Attest:

EDWARD M.FLETCHER,JR.

WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents

